1. Field of the Invention
The invention relates to a one step method for the preparation of alkylphenols from phenol and the corresponding olefin. More particularly it relates to a one-step method for preparation of alkylphenols by reacting phenols and the corresponding olefins over a zeolite molecular sieve catalyst. A particularly effective catalyst is dealuminized Y-zeolite. The method is especially effective in the synthesis of the most desirable para-alkyl phenol, for example, para-nonylphenol, from phenol and nonene.
2. Description of the Related Art
It is known in the art to prepare higher molecular weight alkylphenols, such as p-tert-octylphenol, p-nonylphenol and dodecylphenol by alkylating phenol with diisobutylene, propylene trimer and propylene tetramer, respectively, under acidic conditions. Nonylphenol, in particular, is used as an intermediate for surfactants, as well as antioxidants and lube oil additives.
In "Bisphenol A and Alkylated Phenols", SRI PEP Report No. 192 (December 1988), page 4-4, it is reported that it is known in the art to prepare various alkylphenols by acid catalyzed reactions of phenols with various olefins. These alkylphenols may include p-tert-butylphenol, p-isopropylphenol, p-sec-butylphenol, p-tert-octylphenol, nonylphenol and dodecylphenol. The alkylation reaction takes place at or near atmospheric pressure in the presence of an acidic catalyst such as a mineral acid, a Lewis acid (e.g. boron trifluoride) or a cation exchange resin (e.g. styrene-divinyl benzene resin). The acid catalysts lead to predominantly para-alkylated phenol when the para position is available. Generally a molar ratio of phenol to olefin of 1.5-3:1 is desired to minimize the yield of dialkylphenols.
U.S. Pat. No. 4,198,531, to BASF, discloses a process for continuous manufacture of p-alkylphenols by reacting phenol with olefin at 70.degree.-140.degree. C. in a fixed bed of an organic sulfonic acid cation exchange resin.
A Lewis acid or Bronsted acid catalyst is employed in U.S. Pat. No. 4,096,209 to Ciba-Geigy to prepare a phosphorylated butylated phenol/phenol ester mixture.
In U.S. Pat. No. 2,684,389 to Gulf R & D a phenol and mono-olefin are mixed in the presence of a silica-aluminum adsorbent catalyst at 137.degree. C. A silica-alumina catalyst is also employed in U.S. Pat. No. 3,876,710 to Hitachi to produce PTBP from phenol and isobutylene.
A BF.sub.3 catalyst is used for the reaction of phenol and isobutene in British Patent 1,294,781 to Hoechst where the product cooled to form crystals which are crushed before ammonia is added to remove the catalyst. British Patent 1,249,571 is related.
In German Offen. 3,443,736 to Huels the catalyst is a sulfonated polystyrene ion exchange catalyst. U.S. Pat. No. 4,461,916, also to Huels, discloses a two-stage approach for producing p-tert-octylphenol using an acid ion exchange resin. U.S. Pat. No. 4,236,033 and U.S. Pat. No. 4,168,390 to Huels also disclose ion exchange resins, the latter comprising a LEWATIT.RTM. resin deactivated with Al.sub.2 (SO.sub.4).sub.3.
British Patent 2,120,953 to ICI discloses a process for producing nonylphenol by reacting diisobutene with phenol in the presence of a catalyst comprising fuller's earth with alkyl or aryl phosphate or phosphate ester.
U.S. Pat. No. 3,872,173 to Progil discloses the reaction of gaseous isobutene with liquid phenol in the presence of an acid-activated clay, again in two steps.
A highly acidic aryl sulfonic acid catalyst is employed in U.S. Pat. No. 3,932,537 to react phenol with isobutene under anhydrous conditions.
U.S. Pat. No. 3,422,157 to Union Carbide employs a cation exchange resin catalyst.
British Patent 131,4,623 to Union Rheinische Braunkohlen discloses an activated, acid-free, bleaching earth catalyst.
In U.S. Pat. No. 4,260,833, to UOP, phenol and isobutylene are reacted at 250.degree. C. in the presence of a lithiated alumina catalyst. U.S. Pat. No. 3,929,912 discloses a more general alkylation of phenol and olefins in the presence of hydrogen fluoride and carbon dioxide.
An aluminum phenoxide catalyst is used for the orthoalkylation of phenol with butene-1 in French Patent 2,296,610, and U.S. Pat. No. 3,766,276, to Ethyl, as well as U.S. Pat. No. 3,933,927.
A boron trifluoride catalyst is used for the alkylation of phenol in U.S. Pat. No. 3,317,612.
Activated earth and phosphoric acid are used in a liquid phase transalkylation process in British Patent 1,444,935.
Acids are also useful for the condensation of phenol with acetone. Representative acids include an aromatic sulfonic acid (German Offen. 2,811,182 and U.S. Pat. No. 4,387,251), a volatile acid catalyst (U.S. Pat. No. 2,623,908), a strong mineral acid such as HCl or H.sub.2 SO.sub.4 (U.S. Pat. No. 2,359,242), hydrochloric acid (U.S. Pat. No. 4,517,387), H.sub.2 SO.sub.4 or HCl and 2-(4-pyridyl)ethanethiol (Japanese Kokai 57-118528), concentrated HCl (Japanese Kokai 60-38335) and hydrogen chloride (U.S. Pat. No. 4,169,211).
The SRI PEP Report, supra, does not suggest the use of a zeolite to facilitate this type reaction.